Role of geometrical relaxation in solution of simple molecules exhibiting anomeric effects

被引：19

作者：

Marcos, ES ^{[1
]}

Pappalardo, RR ^{[1
]}

Chiara, JL ^{[1
]}

Domene, MC ^{[1
]}

Martinez, JM ^{[1
]}

Parrondo, RM ^{[1
]}

机构：

[1] CSIC, INST QUIM ORGAN GEN, E-28006 MADRID, SPAIN

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 1996年 / 371卷

关键词：

ab initio; polyelectron populations; rotations; SCRF method;

D O I：

10.1016/S0166-1280(96)04748-3

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The conformational equilibria in the gas phase and in solution of dimethoxymethane (DMM), MeO-C(H-2)-OMe, and dimethoxyethane (DME), MeO-C(HMe)-OMe, have been studied by means of quantum-chemical calculations. The influence of the anomeric effect on these equilibria and their interconversion processes has been investigated. Solvent effects have been described using the continuum cavity model of Nancy's group. Geometry optimizations have been performed in both gas-phase and solution media (water permittivity was used). For DMM, three stable conformers exist, but for DME the potential energy surface in solution shows a new minimum which corresponds to a fourth stable conformer. Energy profiles corresponding to rotation around the C-OMe bond, for interconversion of alpha- and beta-anomers, have been calculated for processes in the gas phase and in solution. One-electron and polyelectron population analyses in terms of the natural hybrid orbitals of Weinhold have been performed to understand the evolution of the electronic structure with torsion about the C-O bonds.

引用

页码：245 / 256

页数：12

共 56 条

[1] ON THE ABINITIO GEOMETRY OPTIMIZATION OF MOLECULAR SOLUTES [J].